Analytical chemistry

PHC 251/202
Handout-10
Precipitation Titration
Precipitation Titration
What is Precipitation Titration:
Precipitation is the process of combination of two ionic species to form
a very insoluble product.
A reaction in which the analyte and titrant form a
insoluble precipitate also can serve as the basis for a
titration. this type of titration a precipitation
titration.
Principle of precipitation:
• Solubility depends on the solvent and the temperature.
• It is the concentrate of the dissolved solute in mole/litre when the
solution is in equilibrium with a solid solute.
• In order to dissolve a solid, solute-solute attraction is replaced by
solute-solvent attraction, i.e., “like dissolve like”.
• But during precipitation, opposite thing happens. Here in
Precipitation intermolecular forces between the molecules of
product are high. So solute-solute forces replace solute-solvent
forces.
 Solubility Product:
Consider a solution of a slightly salt, BA, which is in equilibrium
with the solid phase BA:
BA B+ + A-
(solid) (Solution)

Applying the law of mass action to this system.

K
The concentration of BA will be constant. So, the equilibrium
constant for the equation is:
K = [ B+] + [A-]
K is called solubility product and has a symbol Ksp.
If the salt has general formula BmAneach molecule will give m
cations and n anions.
 What is cations and anions?

Bm A n mB + nA

 And equation is:

Ksp = [ B+]m + [A-]n

• In saturated solution of the slightly soluble salt BA in water

[ B+] = [A-] = Ksp
• Solubility product helps in calculation of one of the ion concentrate if the
the other is known.
• A substance precipitate if the product of the ionic concentrate exceeds Ksp
value.
• This mean that solid BA will precipitate out if the product [ B+] and [A-]
exceeds Ksp.
Example: Calculate the solubility product of of MgCO 3 if 1 litre of its
saturated solution contains 0533 g of MgCO3 at 20C.
Solution:
MgCO3Mg2+ + CO2- 3

Ksp (MgCO3) = [Mg2+] [CO3]2-

Molecular weight of MgCO3 = 84.32
The molar solubility of MgCO3 will be = 0.00632 = 6.32 X 10-3 mole/litre.

 Since each mole of MgCO3 on dissociation forms 1 gm ion of Mg2+and 1 gm ion

of CO2-3

 Mg2+ and CO2- ions in the solution have the same concentration equal to molar
solubility.
[Mg2+] = [CO3]2- = 6.32 X 10-3
Ksp (MgCO3) = [Mg2+] X [CO3]2-

= 6.32 X 10-3 X 6.32 X 10-3

= 4 X 10-6
So, the solubility product of MgCO3 = 4 X 10-6
 Precipitation method Use
• The precipitation method is the one used for the
determination of the amount of calcium in water. Using
this method, an excess of oxalic acid, H2C2O4, is added
to a measured, known volume of water.
• By adding a reagent, here ammonium oxalate, the
calcium will precipitate as calcium oxalate.
• The proper reagent, when added to aqueous solution,
will produce highly insoluble precipitates from the
positive and negative ions that would otherwise be
soluble with their counterparts (equation 1).
The reaction is:
Formation of calcium oxalate:
Ca2+ (aq) + C2O42- → CaC2O4
The precipitate is collected, dried and ignited to high (red) heat
which converts it entirely to calcium oxide.

The reaction is pure calcium oxide formed

CaC2O4 → CaO(s) + CO (g) + CO2 (g)

The pure precipitate is cooled, then measured by weighing, and the

difference in weights before and after reveals the mass of analyte
lost, in this case calcium oxide.
That number can then be used to calculate the amount, or the
percent concentration, of it in the original mix.
Common Ion Effect:
Solubility of any slightly soluble salt can be decreased by adding an excess
of either of its ions.
For example in the following equation an excess of either B+ or A- is added
whose solubility is greater then that of BA then the product of ionic
concentration of [ B+] [A-] will excess the solubility product.
Therefore, [BA] will precipitate.

Example:
If an excess of silver ions is added to saturated solution of AgCl in water
then the solubility product of [Ag] [Cl] is excessed.
Therefore, some Ag (added) and Cl ions will be precipitated as AgCl.

Depression of solubility by the common-ion effect is of fundamental

importance in gravimetric analysis.
 Mohr’s Method
Determination of chloride ion concentration by titration method:
Potassium chromate KCrO4 is used as indicator in the titration of chloride
ions with standard silver nitrate AgNO 3 in neutral solution, giving
precipitate of red silver chromate Ag2CrO4 at the end point.
This method can be used in determination of chloride ion concentration
of water samples from many sources like sea water, river water, tap
water….etc.
Theory:
Here, silver nitrate is slowly added to the solution containing chloride so a
precipitate of AgCl is formed
Ag+(aq) + Cl-(aq) AgCl(s)
When all chloride ions get precipitated, then the addition of silver ions react
with the chromate ions of the indicator (Potassium chromate) giving reddish
brown precipitate of silver chromate and this is the end point.
2Ag+ (aq) + CrO4 (aq) Ag2CrO4 (s)
Silver chromate